US3790646A - Oil-resistant polymer composition - Google Patents
Oil-resistant polymer composition Download PDFInfo
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- US3790646A US3790646A US00247010A US3790646DA US3790646A US 3790646 A US3790646 A US 3790646A US 00247010 A US00247010 A US 00247010A US 3790646D A US3790646D A US 3790646DA US 3790646 A US3790646 A US 3790646A
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- US
- United States
- Prior art keywords
- weight
- acid
- copolymer
- polymer
- latex
- Prior art date
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- Expired - Lifetime
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- 229920000642 polymer Polymers 0.000 title abstract description 44
- 239000000203 mixture Substances 0.000 title abstract description 39
- 229920001577 copolymer Polymers 0.000 abstract description 36
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 24
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 abstract description 20
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 15
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 11
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 description 35
- 239000004816 latex Substances 0.000 description 34
- 229920000126 latex Polymers 0.000 description 34
- 229920001971 elastomer Polymers 0.000 description 21
- 239000005060 rubber Substances 0.000 description 21
- 239000002253 acid Substances 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- 229920002125 Sokalan® Polymers 0.000 description 12
- 150000003863 ammonium salts Chemical class 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000000701 coagulant Substances 0.000 description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- -1 Aluminum Aluminum Aluminum Calcium Calcium sulfate Chemical compound 0.000 description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 230000015271 coagulation Effects 0.000 description 8
- 238000005345 coagulation Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000001112 coagulating effect Effects 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 4
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- MUZDXNQOSGWMJJ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O MUZDXNQOSGWMJJ-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 235000006708 antioxidants Nutrition 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 229920006027 ternary co-polymer Polymers 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229920013646 Hycar Polymers 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 description 1
- 229920008712 Copo Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 238000007696 Kjeldahl method Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- SZKGHIVKMXYMDC-UHFFFAOYSA-N S(=O)(=O)(O)O.Cl.Cl Chemical compound S(=O)(=O)(O)O.Cl.Cl SZKGHIVKMXYMDC-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011953 free-radical catalyst Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- APVPOHHVBBYQAV-UHFFFAOYSA-N n-(4-aminophenyl)sulfonyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 APVPOHHVBBYQAV-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- KYKNRZGSIGMXFH-ZVGUSBNCSA-M potassium bitartrate Chemical compound [K+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O KYKNRZGSIGMXFH-ZVGUSBNCSA-M 0.000 description 1
- 239000001472 potassium tartrate Substances 0.000 description 1
- 229940111695 potassium tartrate Drugs 0.000 description 1
- 235000011005 potassium tartrates Nutrition 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- WYGKOZHQYKSCMW-UHFFFAOYSA-H trialuminum trisulfate Chemical compound [Al+3].[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O WYGKOZHQYKSCMW-UHFFFAOYSA-H 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L13/00—Compositions of rubbers containing carboxyl groups
Definitions
- An oil-resistant polymer composition comprising (I) to 50% by weight of a copolymer consisting essentially of to 50% by weight of acrylonitrile, 50 to 80% by weight of a diene selected from butadiene and isoprene and 0.1 to 10% by weight of an a,fl-ethylenically unsaturated carboxylic acid and having a number average mo lecular weight of about 500 to 10,000 and (II) 95 to 50% by weight of an acrylonitrile/butadiene copolymer.
- This invention relates to an oil-resistant polymer composition, and more specifically to an oil-resistant polymer composition comprising a copolymer composed essentially of acrylonitrile, butadiene or isoprene and an oc, ⁇ 3-ethylenically unsaturated carboxylic acid and an acrylonitrile butadiene copolymer.
- composition comprising 5 to 50% by weight of (I) a copolymer consisting essentially of 20 to 50% by weight of acrylonitrile,
- a diene selected from the group consisting of butadiene and isoprene and 0.1 to 10% by weight of an a,/3-ethylenically unsaturated carboxylic acid and having a number average molecular weight of about 500 to 10,000 and (II) to 50% by weight of an acrylonitrile-butadiene copolymer.
- the polymer composition of this invention can find utility in a wide range of applications which require resistance to highly aromatic solvents. Since the composition of the invention has far superior resistance to solvent crack when compared with conventional acrylonitrilebutadiene copolymer compositions, it can sufliciently withstand use under severe service conditions such as in gasoline having a high aromatic content.
- the low-molecular-weight (about 500 to 10,000) ternary copolymer of acrylonitrile, butadiene or isoprene, and an c p-unsaturated carboxylic acid used in the invention is produced in accordance with a usual emulsion-polymerization recipe.
- the polymerization temperature may be low (about 0 C.) or high (30 to 80 C.). Therefore, the polymerization initiator may be a Redox catalyst or a free-radical catalyst such as potassium persulfate and organic peroxides. Since the polymerization system isacidic, any emulsifier which has an emulsifying action under acidic conditions may be used.
- an aqueous emulsifier solution should be acidified prior to the feeding of monomers.
- a molecular-weight modifier that can be used is a mercaptan such as tertiary dodecyhnercaptan, and its amount is controlled so that a copolymer of the desired low molecular weight can be obtained.
- Chemicals such as the monomers, molecular-weight modifier and emulsifier may be charged any time before the initiation of reaction, or if desired, in divided portions. The polymerization can be employed either batchwise or continuously.
- the a,B-ethylenically unsaturated carboxylic acid at least one monoor dicarboxylic acid selected, for example, from acrylic acid, methacrylic acid, maleic acid and itaconic acid may be used.
- the proportion of the carboxylic acid to be polymerized is from 0.1 to 10% by weight. If the proportion is less than 0.1% by weight, the solvent crack resistance of the polymer composition cannot be improved, and if it exceeds 10% by weight, the solvent crack resistance and other properties are undesirably deteriorated.
- the polymer composition of this invention is an admixture of (I) 5 to 50 parts by Weight of this low-molecularweight polymer and (II) 95 to 50 parts by weight of an ordinary acrylonitrile-butadiene copolymer having an acrylonitrile content of about 20 to 50% by weight, the sum of (I) and (II) being parts by weight. If the amount of copolymer (I) is less than 5 parts by weight, the solvent crack resistance is not improved, and if it exceeds 50 to parts by weight, the mechanical properties of the composition are lowered.
- These two polymers (I) and (II) may be mixed in the form of latex or by a mixer such as roll or Banbury mixer or in a solvent.
- the coagulation of the latex of polymer (1) and that of polymer (II) can be carried out in a customary manner.
- the methods generally in practice involve the use of an inorganic metal salt such as chlorides and sulfates of sodium, calcium, magnesium or aluminum or an organic metal salt such as potassium tartrate as a coagulating agent, with or without the conjoint use of an inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid or silicic acid or an organic acid such as acrylic acid, citric acid or tartaric acid.
- the amount of the metal salt is 1 to 5% based on the solids content of the rubber in the latex, and the amount of the acid is to 6% by weight on the same basis.
- the solvent rack resistance of the composition of this invention can be further improved by using as a coagulation agent an u,fi-ethylenically unsaturated carboxylic acid such as an acrylic acid polymer, a methacrylic acid polymer or an acrylic acid-methacrylic acid copolymer or its ammonium salt and the metal salt in the coagulation of the latex of copolymer (I) or a mixture of the copolymer latex (I) and the copolymer latex (II).
- Thi coagulation agent is especially preferable since it can inhibit the corrosion of metal machinery in the dehydration and drying process. If desired, this coagulation agent can be used conjointly with the above-mentioned known acid.
- the amount of the acid may sufiiciently be as small as up to 2% by weight, and there is substantially no problem of the corrosion of the machinery.
- the polymer of an a,fi-ethylenically unsaturated carboxylic acid used to coagulate the copolymer latex is a polymer or copolymer obtained by polymerizing an oat"?- ethylenically unsaturated monoor dicarboxylic acid having 3 to 5 carbon atoms, such as acrylic acid, methacrylic acid, fumaric acid, maleic acid or itaconic acid, in an aqueous medium using potassium persulfate, ammonium persulfate or a Redox catalyst.
- the acrylic acid polymer, methacrylic acid polymer and acrylic acid/methacrylic acid copolymer are preferred.
- ammonium salts of these polymers obtained by neutralizing them with aqueous ammonia or ammonia to a neutrality of 0 to 1 can also be used. Even when the ammonium salt having a neutrality of l is used, a part of the ammonium salt sometimes remains in the form of an acid depending upon its pH at the time of coagulating the latex.
- the viscosity average degree of polymerization (p) of these polymers or ammonium salts thereof is usually 50 to 200,000, preferably 500 to 20,000.
- the amount of the polymer is 0 to 6% by weight, preferably 0.5 to 3% by weight, based on the solids content of the copolymer in the latex. Amounts in excess of 6% by weight sometimes cause a marked rise in the viscosity of the latex, and are undesirable and uneconomical.
- the order of adding the coagulating agent to the latex is optional.
- the acid polymer is first added to the latex, and the metal salt or the metal salt and the acid are added at the time of coagulation.
- all of the coagulating agents may be added separately.
- the acid polymer especially when the metal is of a divalent nature.
- the acid is used in an increased amount to reduce the pH.
- a coagulating assistant such as glue and polyamine may be conjointly used.
- the coagulation is performed at room tem perature or at an elevated temperature according to the usual method. Subsequent water-washing and drying give a rubber composition.
- the polymer composition so prepared is vulcanized in a customary manner using sulfur or a peroxide.
- ordinary additives such as a reinforcing agent, extender, softening agent, anti-oxidant or pigment can also be added.
- the polymer composition of this invention can be used in a wide variety of fields either alone or in admixture with natural or synthetic rubber in the form of latex or solid, and finds special utility in applications which require good resistance to solvent crack, such as the production of fuel hoses, packings, oil seals, gaskets, belts, rolls for spinning frames, printing rolls or diaphragms.
- EXAMPLE 1 Polymerization was carried out in accordance with the recipe shown in Table 1 using an autoclave having an inner capacity of about 12 liters at C. until the conversion of the monomer reached 85%. After completion of the reaction, a commercially available anti-oxidant was added to the latex, and the polymer latex was coagulated with an aqueous solution of aluminum sulfate, followed by washing with water and drying in a vacuum dryer to form a liquid copolymer. The combined acrylonitrile content (percent) of the resulting copolymer was measured by the Kjeldahl method. The combined carboxyl group content (moles of COO-H per 100 parts of rubber) was determined by the titration method. The number average molecular weight was measured by an ebulliometer. The properties of the polymer are shown in Table 2.
- Acrylic acid was used instead of methacrylic acid.
- b Isoprene was used instead of butadiene.
- Indicator lines were drawn at intervals of 10 mm. on a rectangular test piece 10 mm. wide and 2 mm. thick. Midway between two adjoining indicator lines a crack 2 mm. thick was provided by a razor in a direction parallel to the indicator lines extending to the back thereof.
- the test piece was mounted to jigs capable of being extended at a stretch ratio of 100%. At this time, the distance between the jigs was adjusted constantly to 30 mm.
- the test piece was in a taut state in a test solvent (a mixture of iso-octane/ toluene in a volume ratio of 40:60) at 30 C., and the time that elapsed until the break of the sample was measured.
- the acrylonitrile-butadiene co- EXAMPLE 2 polymer alone has poor resistance to solvent crack.
- the solvent crack resistance of a mixture of the acrylonitrilebutadiene copolymer with a liquid copolymer free from a carboxyl group can be improved only to a slight extent (see Experiment No. 2).
- the polymer compositions of the present invention (Examples Nos. 3 to 6) have extremely good solvent crack resistance.
- Polymerization was performed at 5 C. in accordance with the polymerization recipe shown in Table 6 below. When the conversion reached at least 85%, a short stop was added to stop the polymerization reaction, followed by addition of a commercially available antioxidant to form a latex having a combined acrylonitrile content of 42.5% and a Mooney viscosity (100 C. ML of 65.0.
- a aqueous solution of acrylic acid polymer (Aron A(H) degree of polymerization about 2000 (product of Tea Gosei Kagaku Kogyo Co., Ltd.) was admixed with the latex in advance, and a 0.3% aqueous solution of a metal salt was admixed with such latex at the time of the coagulation treatment, whereby the latex was coagulated at to C.
- the resulting crumb was washed with water, 'and dried in vacuo at C. for 24 hours to form a rubber. This rubber was compounded on a roll in accordance with the receipe shown in Table 7.
- Example 3 The procedure of Example 2 was repeated except that 25 the coagulating agent used was changed as shown in Table 9. The solvent crack resistance was measured at 2'0 C. and 40 C. The results obtained are shown in Table 9.
- the solvent crack resistance of the resulting vulcanized product and its physical properties are shown in Table 8.
- the amount of the coagulating agent in the following As is seen from Table 9, the use of the acrylic acid polymer as a coagulating agent together with the metal salt and acid gives rise to greater improvement of the solvent crack resistance of the vulcanized rubber composition.
- EXAMPLE 4 The mixed latex prepared in Example 2 was coagulated using a coagulating agent shown in Table 10 and washed with water. The resulting rubber crum containing about 40% of water was held between steel plates (SAE-IOZO), and allowed to stand in a gear oven for 20 hours at C. The crumb and the steel plates were taken out, and the corrosion of the surfaces of the steel plates was judged by the naked eye. The results are shown in Table 10.
- EXAMPLE 5 5 In accordance with the polymerization recipe shown in EXAMPLE Table 11, polymerization was performed at 35 C. When the conversion reached at least 85%, a short stop was The PFOcedllre fEXaII ⁇ P1e Was repeated except that added to stop the reaction. Then, a commercially avail- Coagulatlng agent shown In Table 13 was used- The P bl ti id t was dd d t f a latex h i a erties of the resulting vulcanized product were rated. The combined acrylonitrile content of 42.3% and a Mooney resistance to solvent crack was measured at 17 C. and
- Example 4 Sodium alkylbenzenesulfonate 1.0 s di Sulf t 0.2 The procedure of Example 4 was repeated using the Potassium persulfate 0.3 mixed latex employed in Example 5, and using the co- Tertiary dodecyl mercaptan 0.52 agulating agents indicated in Table 14.
- Acid or ammonium salt (2.7 parts)--- Sulfuric acid Hydrochloric acid Ammonium salt of the acrylic acid polymer. Extent of corrosion of the steel plate Large Large Small.
- a 5% aqueous solution of the ammonium salt of an What is claimed is: acrylic acid P y (Aron A30, degree of P Y 1.
- An oil-resistant polymer composition consisting estion about 2500, neutrality 1, product of Toa Gosei sentially of (I) 5 to by weight of a ternary copo1y Kagaku Kogyo J was admlxed wlth the above 50 mer consisting essentially of 20 to 50% by weight of mixed latex 1n advance and a 03% aqueous 9 of acrylonitrile, 50 to 80% by weight of a diene selected from the metal salt was added to the latex at the time of cobutadiene and isoprene and (M to 10% by weight of an agulanona treatment whereby the latex was f i at a,,8-ethylenically unsaturated monoor di-carboxylic acid 30 to 40
- the resultmg crumb was Washe
- liquid copolymer being prepared by coagulating a TABLE 12 ternary copolymer latex with a number average molecular weight of about 500 to 10,000 consisting essentially of 20 Experiment No. to 50% by weight of acrylonitrile, 50 to 80% by weight 1 (control) 2 3 of a diene selected from butadiene and isoprene and 0.1 ii iiiiii fiiae Aluminum Aluminum Calcium to 10% by weight of an a,fl-ethylenically unsaturated Amount ammonium Salt of sulfate Sulfate cmmde monoor di-carboxylic acid selected from acrylic acid, t g gg y c a d polymer 0 1.8 1.8 methacrylic acid, maleic acid and itaconic acid, 1n the properges 5f 1551 135555 presence of a metal chloride, sulfate or tartrate and a gggg f strength 134 polymer of an a,B-
- composition of claim 2 wherein said metal salt is aluminum sulfate or calcium chloride, and said ,5- ethylenically unsaturated carboxylic acid polymer is poly- (acrylic acid).
- An oil-resistant polymer composition consisting essentially of one obtained by mixing 5 to 50% by weight as solids content of (I) a latex of a ternary copolymer of a number average molecular weight of about 500 to 10,000 consisting essentially of to by weight of acrylonitrile, 50 to by weight of a diene selected from butadiene and isoprene and 0.1 to 10% by weight of an e,fl-ethylenically unsaturated monoor di-carboxylic acid with to 50% by weight as solids content and (II) a latex of an acrylonitrile/butadiene copolymer, and coagulating the resulting mixed latex in the presence of a metal chloride, sulfate or tartrate and an a tiethylenically unsaturated carboxylic acid polymer selected from poly(acrylic acid), poly(methacrylic acid) and an acrylic acid-methacrylic acid copolymer or its ammonium salt.
- composition of claim 4 wherein said metal salt is aluminum sulfate or calcium chloride, and said a,;3-'
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Abstract
AN OIL-RESISTANT POLYMER COMPOSITION COMPRISING (1) 5 TO 50% BY WEIGHT OF A COPOLYMER CONSISTING ESSENTIALLY OF 20 TO 50% BY WEIGHT OF ACRYLONITRILE, 50 TO 80% BY WEIGHT OF A DIENE SELECTED FROM BUTADIENE AND ISOPRENE AND 0.1 TO 10% BY WEIGHT OF AN A,B-ETHYLENICALLY UNSATURATED CARBOXYLIC ACID AND HAVING A NUMBER AVERAGE MOLECULAR WEIGHT OF ABOUT 500 TO 10,000 AND (II) 95 TO 50% BY WEIGHT OF AN ACRYLONITRILE/BUTADIENE COPOLYMER.
Description
United States Patent US. Cl. 260-894 6 Claims ABSTRACT OF THE DISCLOSURE An oil-resistant polymer composition comprising (I) to 50% by weight of a copolymer consisting essentially of to 50% by weight of acrylonitrile, 50 to 80% by weight of a diene selected from butadiene and isoprene and 0.1 to 10% by weight of an a,fl-ethylenically unsaturated carboxylic acid and having a number average mo lecular weight of about 500 to 10,000 and (II) 95 to 50% by weight of an acrylonitrile/butadiene copolymer.
This invention relates to an oil-resistant polymer composition, and more specifically to an oil-resistant polymer composition comprising a copolymer composed essentially of acrylonitrile, butadiene or isoprene and an oc,}3-ethylenically unsaturated carboxylic acid and an acrylonitrile butadiene copolymer.
When rubberis used in a state of contact with chemicals or solvents, changes in the volume, strength and elasticity modulus become important problems, and these phenomena are being investigated as important subjects. Rubber compositions have been selected for practical purposes so that these properties are suitable for the desired end use.
When rubber comes in contact with a solvent, it is frequently broken within a short period of time under a low stretch which would not cause breakage in air. This phenomenon of crack growth in a solvent is known as solvent crack in the field of plastics. However, there have been only a few reports on studies made on this phenomenon in rubber.
The occurrence of solvent crack should naturally be avoided in the case of rubber materials to. be used in contact with gasoline, and therefore rubber compositions based mainly on an acrylonitrile-butadiene copolymer are widely used. As a result of the social demand for excluding a lead ingredient from gasoline, it is expected that the content of an aromatic ingredient (the aromatic content of gasoline now in use is estimated at about 50%) will be increased. The solvent crack phenomenon would therefore becomes a practical problem even with the acrylonitrile-butadiene copolymer compositions. Having assumed such a situation, extensive investigation has been 5 conducted on the solvent crack phenomenon of rubber in a mixed solvent of iso-octane and toluene in a ratio of 40:60. As a result, it has been found that a standard acrylonitrile-butadiene copolymer composition now in wide use has a crack break life, as measured under the conditions to be described, of only less than one minute, and cannot withstand practical use.
It is therefore an object of this invention to provide an oil-resistant polymer composition which undergoes extremely small crack growth when in contact with highly aromatic solvents.
Other objects of this invention will become apparent from the following description.
According to this invention, a composition is provided comprising 5 to 50% by weight of (I) a copolymer consisting essentially of 20 to 50% by weight of acrylonitrile,
50 to by weight of a diene selected from the group consisting of butadiene and isoprene and 0.1 to 10% by weight of an a,/3-ethylenically unsaturated carboxylic acid and having a number average molecular weight of about 500 to 10,000 and (II) to 50% by weight of an acrylonitrile-butadiene copolymer.
When the polymer composition was tested as to it solvent crack phenomenon under the conditions to be described, it was found to have a crack break life of longer than about 5 minutes, thus showing a great improvement. Therefore, the polymer composition of this invention can find utility in a wide range of applications which require resistance to highly aromatic solvents. Since the composition of the invention has far superior resistance to solvent crack when compared with conventional acrylonitrilebutadiene copolymer compositions, it can sufliciently withstand use under severe service conditions such as in gasoline having a high aromatic content.
The low-molecular-weight (about 500 to 10,000) ternary copolymer of acrylonitrile, butadiene or isoprene, and an c p-unsaturated carboxylic acid used in the invention is produced in accordance with a usual emulsion-polymerization recipe. The polymerization temperature may be low (about 0 C.) or high (30 to 80 C.). Therefore, the polymerization initiator may be a Redox catalyst or a free-radical catalyst such as potassium persulfate and organic peroxides. Since the polymerization system isacidic, any emulsifier which has an emulsifying action under acidic conditions may be used. It is preferred that an aqueous emulsifier solution should be acidified prior to the feeding of monomers. Typical examples of a molecular-weight modifier that can be used is a mercaptan such as tertiary dodecyhnercaptan, and its amount is controlled so that a copolymer of the desired low molecular weight can be obtained. Chemicals such as the monomers, molecular-weight modifier and emulsifier may be charged any time before the initiation of reaction, or if desired, in divided portions. The polymerization can be employed either batchwise or continuously. As the a,B-ethylenically unsaturated carboxylic acid, at least one monoor dicarboxylic acid selected, for example, from acrylic acid, methacrylic acid, maleic acid and itaconic acid may be used. The proportion of the carboxylic acid to be polymerized is from 0.1 to 10% by weight. If the proportion is less than 0.1% by weight, the solvent crack resistance of the polymer composition cannot be improved, and if it exceeds 10% by weight, the solvent crack resistance and other properties are undesirably deteriorated.
The polymer composition of this invention is an admixture of (I) 5 to 50 parts by Weight of this low-molecularweight polymer and (II) 95 to 50 parts by weight of an ordinary acrylonitrile-butadiene copolymer having an acrylonitrile content of about 20 to 50% by weight, the sum of (I) and (II) being parts by weight. If the amount of copolymer (I) is less than 5 parts by weight, the solvent crack resistance is not improved, and if it exceeds 50 to parts by weight, the mechanical properties of the composition are lowered. These two polymers (I) and (II) may be mixed in the form of latex or by a mixer such as roll or Banbury mixer or in a solvent.
The coagulation of the latex of polymer (1) and that of polymer (II) can be carried out in a customary manner. The methods generally in practice involve the use of an inorganic metal salt such as chlorides and sulfates of sodium, calcium, magnesium or aluminum or an organic metal salt such as potassium tartrate as a coagulating agent, with or without the conjoint use of an inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid or silicic acid or an organic acid such as acrylic acid, citric acid or tartaric acid. The amount of the metal salt is 1 to 5% based on the solids content of the rubber in the latex, and the amount of the acid is to 6% by weight on the same basis. The solvent rack resistance of the composition of this invention can be further improved by using as a coagulation agent an u,fi-ethylenically unsaturated carboxylic acid such as an acrylic acid polymer, a methacrylic acid polymer or an acrylic acid-methacrylic acid copolymer or its ammonium salt and the metal salt in the coagulation of the latex of copolymer (I) or a mixture of the copolymer latex (I) and the copolymer latex (II). Thi coagulation agent is especially preferable since it can inhibit the corrosion of metal machinery in the dehydration and drying process. If desired, this coagulation agent can be used conjointly with the above-mentioned known acid. In this case, the amount of the acid may sufiiciently be as small as up to 2% by weight, and there is substantially no problem of the corrosion of the machinery.
The polymer of an a,fi-ethylenically unsaturated carboxylic acid used to coagulate the copolymer latex is a polymer or copolymer obtained by polymerizing an oat"?- ethylenically unsaturated monoor dicarboxylic acid having 3 to 5 carbon atoms, such as acrylic acid, methacrylic acid, fumaric acid, maleic acid or itaconic acid, in an aqueous medium using potassium persulfate, ammonium persulfate or a Redox catalyst. The acrylic acid polymer, methacrylic acid polymer and acrylic acid/methacrylic acid copolymer are preferred. The ammonium salts of these polymers obtained by neutralizing them with aqueous ammonia or ammonia to a neutrality of 0 to 1 can also be used. Even when the ammonium salt having a neutrality of l is used, a part of the ammonium salt sometimes remains in the form of an acid depending upon its pH at the time of coagulating the latex.
It is to be noted in this connection that these acid polymers and their ammonium salts are usually employed as binders, cosmetics, aqueous paints, adhesives, thickners, etc.
The viscosity average degree of polymerization (p) of these polymers or ammonium salts thereof (as determined by the method described in Herman F. Mark, Encyclopedia of Polymer Science and Technology, vol. 1, page 216, 1964) is usually 50 to 200,000, preferably 500 to 20,000. The amount of the polymer is 0 to 6% by weight, preferably 0.5 to 3% by weight, based on the solids content of the copolymer in the latex. Amounts in excess of 6% by weight sometimes cause a marked rise in the viscosity of the latex, and are undesirable and uneconomical.
The order of adding the coagulating agent to the latex is optional. For example, the acid polymer is first added to the latex, and the metal salt or the metal salt and the acid are added at the time of coagulation. Or all of the coagulating agents may be added separately. However,
acid polymer, especially when the metal is of a divalent nature. To overcome this problem, the acid is used in an increased amount to reduce the pH. If required, a coagulating assistant such as glue and polyamine may be conjointly used. The coagulation is performed at room tem perature or at an elevated temperature according to the usual method. Subsequent water-washing and drying give a rubber composition.
The polymer composition so prepared is vulcanized in a customary manner using sulfur or a peroxide. In addition to the vulcauizing agent, ordinary additives such as a reinforcing agent, extender, softening agent, anti-oxidant or pigment can also be added.
The polymer composition of this invention, like the ordinary acrylonitrile-butadiene copolymer, can be used in a wide variety of fields either alone or in admixture with natural or synthetic rubber in the form of latex or solid, and finds special utility in applications which require good resistance to solvent crack, such as the production of fuel hoses, packings, oil seals, gaskets, belts, rolls for spinning frames, printing rolls or diaphragms.
The invention will now be described specifically by the following non-limitative examples. In each of the examples, all parts and percentages are by weight.
EXAMPLE 1 Polymerization was carried out in accordance with the recipe shown in Table 1 using an autoclave having an inner capacity of about 12 liters at C. until the conversion of the monomer reached 85%. After completion of the reaction, a commercially available anti-oxidant was added to the latex, and the polymer latex was coagulated with an aqueous solution of aluminum sulfate, followed by washing with water and drying in a vacuum dryer to form a liquid copolymer. The combined acrylonitrile content (percent) of the resulting copolymer was measured by the Kjeldahl method. The combined carboxyl group content (moles of COO-H per 100 parts of rubber) was determined by the titration method. The number average molecular weight was measured by an ebulliometer. The properties of the polymer are shown in Table 2.
Potassium persulfate 0.3 Tertiary dodecylmercaptau (varying amounts, see
Table 2).
TABLE 2 Polymerization conditions Properties of the polymer Amounts of monomers charged (parts) Amount of tert.- Combined Combined Number dodeeylacrylocarboxyl average Acrylo- Methaeryllc mercaptan mtrile group molecular mtnle Butadiene acid (parts) (percent) (ephn) weight 10. 0 42. 5 1, 880 45 54. 5 0. 5 10. 0 42. t 0. 005 1, 910 45 53 2. 0 10. 0 43. 1 0. 022 1, 870 45 48. 5 6. 5 10. 0 43. 5 0. 075 2, 020 45 45 10. 0 10. 0 43. 2 0. 110 1, 980 35 63 2. 0 9.0 33. 8 0.024 1, 930 so so 12. 0 45. s 1, sec 50 48 2. 0 12. 0 4.5. 2 0. 021 1, 910 45 53 2. 0 17.0 42.5 0.023 1,150 45 58 2. 0 3. 5 42.8 0. 023 6,010 45 53 l 2. O 10. 0 43. 3 0. 025 1, 980 45 b 53 2. 0 10. 0 43. 2 0. 022 2, 020
I Acrylic acid was used instead of methacrylic acid. b Isoprene was used instead of butadiene.
when the acid is mixed with the metal salt prior to addi- 100 parts of a mixture of the resulting liquid copolymer tion, both react with each other to form a water-insoluble and a commercially available acrylonitrile-butadiene copolymer, 5 parts of zinc oxide, 1 part of stearic acid, 0.3 part of sulfur, 65 parts of FEF carbon black, parts of dioctyl phthalate, and parts of tetramethyl thiuram monosuliide were mixed on a roll and the mixture was vulcanized for minutes at 150 C. The properties and the solvent crack resistance of the resulting vulcanized products are shown in Tables 3 to 5.
The measurement of the solvent crack resistance was made as follows:
Indicator lines were drawn at intervals of 10 mm. on a rectangular test piece 10 mm. wide and 2 mm. thick. Midway between two adjoining indicator lines a crack 2 mm. thick was provided by a razor in a direction parallel to the indicator lines extending to the back thereof. The test piece was mounted to jigs capable of being extended at a stretch ratio of 100%. At this time, the distance between the jigs was adjusted constantly to 30 mm. The test piece was in a taut state in a test solvent (a mixture of iso-octane/ toluene in a volume ratio of 40:60) at 30 C., and the time that elapsed until the break of the sample was measured.
As is seen from the data shown in Table 5, polymer compositions having excellent resistance to solvent crack can be obtained when the molecular weight of the liquid copolymer Was changed (Experiments Nos. 14 and 15), when acrylic acid was used instead of methacrylic acid (Experiment No. 16), and when isoprene was used in stead of butadiene (Experiment No. 17).
TABLE 3 Experiment No.
1 (con- 2 (control) trol) 3 4 5 6 Amount in parts of acrylonitrile butadiene copolymer 100 80 80 80 80 80 Liquid copolymer:
Sample No A B C D E Parts 20 20 20 20 20 Properties of the vulcanized product:
Tensile strength (kg/cm!) 171 139 142 146 158 167 Elongation (percent) 480 530 470 460 480 420 300% modulus (kg./cm.=) 137 106 108 110 114 124 Hardness (J'IS) 67 63 65 64 68 69 Resistance to solvent crack (break tim 0'43" 1'54 4'41" 1204" 1045" 9'23" I Hycar 1041 (product 0! Nippon Zeon 00., Ltd.).
As is seen from Table 3, the acrylonitrile-butadiene co- EXAMPLE 2 polymer alone has poor resistance to solvent crack. The solvent crack resistance of a mixture of the acrylonitrilebutadiene copolymer with a liquid copolymer free from a carboxyl group can be improved only to a slight extent (see Experiment No. 2). By contrast, the polymer compositions of the present invention (Examples Nos. 3 to 6) have extremely good solvent crack resistance.
Polymerization was performed at 5 C. in accordance with the polymerization recipe shown in Table 6 below. When the conversion reached at least 85%, a short stop was added to stop the polymerization reaction, followed by addition of a commercially available antioxidant to form a latex having a combined acrylonitrile content of 42.5% and a Mooney viscosity (100 C. ML of 65.0.
TABLE 4 Experiment N o. 0 12 (con- 7 8 trol) 1o 11 ml) 13 Amount of acrylonitrile-butadlene copolymer (parts) 90 80 80 80 Amount of acrylonltrile-butadlene copolymer (parts) a. 100 80 Liquid copolymer:
ample N n C C C F G H am 10 4o 20 2o 20 20 Properties of the vulcanlz Tensile strength (kg 149 126 166 143 162 142 139 Elongation (percent) 480 520 610 490 460 610 470 300% modulus (kg. 120 94 141 us 109 10s 11s Hardness (-TIS)- 8 63 69 67 63 66 Resistance to solvent crack (break time) 9'13" 17'29" 0'58" 1047" 8'51" 1'39" 12'07" I Hycar 1041. b Hyear 1042 (product of Nippon Zoom Co., Ltd).
TABLE 6 Parts 65 Acrylonitrile 45 As is seen from the results shown in Table 4, polymer gggi g? compositions having excellent resistance to solvent crack Sodium alkylnaphthalenesulfonate': 1.5 can be obtained when the mixing proportlons of the llqlll Sodium alkylbenzenesulfonate 2.0 copolymers were changed (Experiment Nos. 7, 8 and 4), Sodlum y) Phosphate and when the combined acrylonitrile content of the acrylo- Ferrfms sulfate 1H b 1 th b l Tertiary dodecyl mercaptan 0.50 lene copo ymer or e car oxy group-co Sodium ethylenediaminetetraacetate 0,03 ta g llqmd copolymer was changed (Experlments Sodium formaldehyde sulfoxylate 6 10, 11 and 13). i p-Methane hydroperoxide 0.05
A mixture of 80 parts by weight (as rubber solids content) of this latex and 20 parts by Weight (as rubber 8 tables is based on 100 partsby weight of the rubber solids content of the latex. 1
TABLE 8 I Experiment No.
1 (control) 2 3 4 5 Coag'nlating agent:
Metal salt (2.7 parts) Aluminum Aluminum Aluminum Calcium Calcium sulfate sullate sulfate chloride chloride Amount of the acrylic and polymer..... 0. 9 1. B 1. 8 2. 7 Properties of the vulcanization product:
Tensile strength (kg/cm?) 124 117 118 125 130 Elongation (percent) 410 420 440 410 440 300% modulus (kg/cull).-." 10B 94 94 105 103 Hardness (J IS) 66-59 65-57 68-57 67-57 7055 Resistance to solvent crack a Y O slog! 7123!! eloafl fillsll 6I46II 0155i! 2I15II 2'08 2'16 1l'43ll solids content) of latex C obtained in Example 1 was coagulated using a coagulating agent shown in Table 8. A aqueous solution of acrylic acid polymer (Aron A(H) degree of polymerization about 2000 (product of Tea Gosei Kagaku Kogyo Co., Ltd.) was admixed with the latex in advance, and a 0.3% aqueous solution of a metal salt was admixed with such latex at the time of the coagulation treatment, whereby the latex was coagulated at to C. The resulting crumb was washed with water, 'and dried in vacuo at C. for 24 hours to form a rubber. This rubber was compounded on a roll in accordance with the receipe shown in Table 7. The
20 canized rubber composition.
EXAMPLE 3 The procedure of Example 2 was repeated except that 25 the coagulating agent used was changed as shown in Table 9. The solvent crack resistance was measured at 2'0 C. and 40 C. The results obtained are shown in Table 9.
TABLE 9 Experiment No.
1 (control) 2 Calcium chloride (2.7) Calcium chlorid 2.7 coagulating agents (parts) -.{Suliuric acid (0.9) iulfuric acid Properties of the vulcanized products: Bryhc mud polymer (0'9); Tensile strength (kg/cm!) 119 114. Elongation (percent).-. 500 560. %00%dnmod1(1})(kg./cm-') 93 80.
m- 058 68-61- Resistance to solvent crack at- 6357 compounded composition was vulcanized for 10 minutes at 160 C.
The solvent crack resistance of the resulting vulcanized product and its physical properties are shown in Table 8. The amount of the coagulating agent in the following As is seen from Table 9, the use of the acrylic acid polymer as a coagulating agent together with the metal salt and acid gives rise to greater improvement of the solvent crack resistance of the vulcanized rubber composition.
EXAMPLE 4 The mixed latex prepared in Example 2 was coagulated using a coagulating agent shown in Table 10 and washed with water. The resulting rubber crum containing about 40% of water was held between steel plates (SAE-IOZO), and allowed to stand in a gear oven for 20 hours at C. The crumb and the steel plates were taken out, and the corrosion of the surfaces of the steel plates was judged by the naked eye. The results are shown in Table 10.
TABLE 10 Experiment No. v
1 (control) 2 (control) 3 (control) 1 r 4 Co ting ent: V I Y I v a.
etalsalt 2.7 parts) Aluminum sulfate......-...-. Aluminumsultate Aluminum suli'ate.-.'.. Aluminumsuliate. Acid (2.7 nart Sulfuric avid Phosphoric acidu Hydrochloric acid" crylic acid polymer. corrosionofthe p g Considerablylarge Large Small. I
It is seen from Table 10 that the use of an acrylic acid It is seen from Table 12 that the use of an ammonium polymer as one component of the coagulating agent leads salt of the acrylic acid polymer as one component of the to a remarkable improvement in the corrosion of steel by coagulating agent gives rise to a rubber vulcanized prodthe rubber crumb. uct having superior resistance to solvent crack.
EXAMPLE 5 5 In accordance with the polymerization recipe shown in EXAMPLE Table 11, polymerization was performed at 35 C. When the conversion reached at least 85%, a short stop was The PFOcedllre fEXaII}P1e Was repeated except that added to stop the reaction. Then, a commercially avail- Coagulatlng agent shown In Table 13 Was used- The P bl ti id t was dd d t f a latex h i a erties of the resulting vulcanized product were rated. The combined acrylonitrile content of 42.3% and a Mooney resistance to solvent crack was measured at 17 C. and
viscosity (100 C. ML of 57.5. 40 C. The results are shown in Table 13.
TABLE 13 Experimental report 1 (control) 2 Calcium chloride (4) Calcium chloride (2.7). coagulating agent (parts) Sulfuric acid (0.9).. Sulfuric acid (0.9).
Ammonium salt of acrylic acid polymer (0.9). Properties of the vulcamzed product:
Tensile strength (kg/cm?) 113.. 109. Elongation (percent) 490 560. 300% Modulus (kgJcmfi) 98- 94. Hardness (JIS)-.. 68-e1 63-57. Resistance to solvent crack at- TABLE 11 It is seen from Table 13 that the use of an ammonium Parts salt in an acrylic acid polymer together with the metal Acrylonitrile 5 salt and acid gives rise to greater improvement of the Butadiene 55 solvent crack resistance. Water 250 Sodium alkylnaphthalenesulfonate 2.5 EXAMPLE 7 Sodium alkylbenzenesulfonate 1.0 s di Sulf t 0.2 The procedure of Example 4 was repeated using the Potassium persulfate 0.3 mixed latex employed in Example 5, and using the co- Tertiary dodecyl mercaptan 0.52 agulating agents indicated in Table 14.
TABLE 14 Experiment No.
1 (control) 2 (control) 3 C ti t:
il iai ii ff parts) Aluminum sulfate Aluminum sulfate Aluminum sulfate.
Acid or ammonium salt (2.7 parts)--- Sulfuric acid Hydrochloric acid Ammonium salt of the acrylic acid polymer. Extent of corrosion of the steel plate Large Large Small.
A mixture of 80 parts by weight (as rubber solids con- It is seen from Table 14 that the use of an ammonium t nt) of this latex with 20 parts by weight of latex C salt of the acrylic acid polymer as one component of the obtained in Example 1 was coagulated using a coagulatcoagulating agent gives rise to a remarkable improvement ing agent shown in Table 12. in the extent of corrosion of the steel plate by rubber.
A 5% aqueous solution of the ammonium salt of an What is claimed is: acrylic acid P y (Aron A30, degree of P Y 1. An oil-resistant polymer composition consisting estion about 2500, neutrality 1, product of Toa Gosei sentially of (I) 5 to by weight of a ternary copo1y Kagaku Kogyo J was admlxed wlth the above 50 mer consisting essentially of 20 to 50% by weight of mixed latex 1n advance and a 03% aqueous 9 of acrylonitrile, 50 to 80% by weight of a diene selected from the metal salt was added to the latex at the time of cobutadiene and isoprene and (M to 10% by weight of an agulanona treatment whereby the latex was f i at a,,8-ethylenically unsaturated monoor di-carboxylic acid 30 to 40 The resultmg crumb was Washe wlt water selected from acrylic acid, methacrylic acid, maleic acid and dried in vacuo for 24 hours at 50 C. Thereafter the resulting rubber was compounded on a ton in accord: and itaconic ac1d, and having a number average molecular ance with the compounding recipe shown in Table 7 weight of about 500 to 10,000 and (H) 95 to 50% by above, and then press-vulcanized at 160 C. for 10 min- Weight of afilylonitfik/butadiene P Y utes. The properties and the resistance to solvent crack AH oll-reslstant P y composltlon conslstmg of the resulting vulcanized products are shown in sentially of (I) 5 to 50% by weight of a liquid copolymer,
Table 12, said liquid copolymer being prepared by coagulating a TABLE 12 ternary copolymer latex with a number average molecular weight of about 500 to 10,000 consisting essentially of 20 Experiment No. to 50% by weight of acrylonitrile, 50 to 80% by weight 1 (control) 2 3 of a diene selected from butadiene and isoprene and 0.1 ii iiiiiii fiiae Aluminum Aluminum Calcium to 10% by weight of an a,fl-ethylenically unsaturated Amount ammonium Salt of sulfate Sulfate cmmde monoor di-carboxylic acid selected from acrylic acid, t g gg y c a d polymer 0 1.8 1.8 methacrylic acid, maleic acid and itaconic acid, 1n the properges 5f 1551 135555 presence of a metal chloride, sulfate or tartrate and a gggg f strength 134 polymer of an a,B-ethylenically unsaturated carboxyl c l ngation (perce t) 430 500 47 acid selected from poly(acrylic acid), po1y(methacryl1c gfigggg gl gflfifffg? ig: A9? 67329 acid) and an acrylic acid-methacrylic acid copolymer or to ffi ?fi i 1 1 its ammonium salt and t0 Of an 40 C 0' 0" 2' 75 acrylonitrile/butadiene copolymer.
3. The composition of claim 2 wherein said metal salt is aluminum sulfate or calcium chloride, and said ,5- ethylenically unsaturated carboxylic acid polymer is poly- (acrylic acid).
4. An oil-resistant polymer composition consisting essentially of one obtained by mixing 5 to 50% by weight as solids content of (I) a latex of a ternary copolymer of a number average molecular weight of about 500 to 10,000 consisting essentially of to by weight of acrylonitrile, 50 to by weight of a diene selected from butadiene and isoprene and 0.1 to 10% by weight of an e,fl-ethylenically unsaturated monoor di-carboxylic acid with to 50% by weight as solids content and (II) a latex of an acrylonitrile/butadiene copolymer, and coagulating the resulting mixed latex in the presence of a metal chloride, sulfate or tartrate and an a tiethylenically unsaturated carboxylic acid polymer selected from poly(acrylic acid), poly(methacrylic acid) and an acrylic acid-methacrylic acid copolymer or its ammonium salt.
5. The composition of claim 4 wherein said metal salt is aluminum sulfate or calcium chloride, and said a,;3-'
References Cited UNITED STATES PATENTS 6/1945 'Semon et al 260-941 A 11/1962 Frank 260-894 MURRAY TILLMAN, Primary Examiner I. ZIEGLER, Assistant Examiner US. Cl. X.R.
26029.1 R, 29.7 D, PT, 94.7 R
UNITED sTATEsPATENT OFFICE CER'lIF'lCA'IE OF CORRECIIGN Patent NO. 3,790,646 Dated February 5, 1974 Inventor(s) .Tetsu OHISHI ET AL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as. shown below:
In the Heading, insert the following: Assignors to pp Zeon Tokyo Japan, a corporation of Japan Signed .and sealed this 13th day ofi-A'ugust 197 4.
(SEAL) Attest:
MCCOY M. GIBSON, JR'. 7 o C. MARSHALL DANN Attesting Officer Commissioner of Patents FORM PO-IOSD (10-69) USCOMM-DC 60376- Ff69 U.5. GOVERNMED" PRINTING OFFICE: U, O-OfiQ-JAQ
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2858471A JPS5027486B1 (en) | 1971-05-01 | 1971-05-01 | |
JP8803171A JPS5510601B2 (en) | 1971-11-05 | 1971-11-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3790646A true US3790646A (en) | 1974-02-05 |
Family
ID=26366720
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00247010A Expired - Lifetime US3790646A (en) | 1971-05-01 | 1972-04-24 | Oil-resistant polymer composition |
Country Status (5)
Country | Link |
---|---|
US (1) | US3790646A (en) |
CA (1) | CA966597A (en) |
FR (1) | FR2135567B1 (en) |
GB (1) | GB1375509A (en) |
IT (1) | IT955183B (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3128993A1 (en) * | 1980-07-22 | 1982-04-08 | Japan Synthetic Rubber Co., Ltd., Tokyo | Rubber composition |
US4370440A (en) * | 1979-11-09 | 1983-01-25 | Polysar Limited | Compositions comprising chlorosulphonated polyethylene, carboxylated butadiene-acrylonitrile and magnesium oxide useful for liners or membranes |
DE3248378A1 (en) * | 1981-12-28 | 1983-07-14 | Nippon Zeon Co., Ltd., Tokyo | Oil- and degradation-resistant rubber article |
US4849295A (en) * | 1987-12-11 | 1989-07-18 | Eagle-Picher Industries, Inc. | High temperature metal rubber gasket |
DE3941904A1 (en) * | 1989-12-13 | 1991-06-20 | Inst Hydravlika I Pnevmatika | Elastomer compsn. for hydraulic accumulator balloons - contains acrylonitrile]-butadiene] rubber, carbon black, DBP, zinc oxide, sulphur etc. and specified mixt. of accelerators |
EP3034518A1 (en) * | 2014-12-19 | 2016-06-22 | Lanxess Deutschland GmbH | Color stable nitrile rubbers |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4177074A (en) * | 1978-01-25 | 1979-12-04 | E. I. Du Pont De Nemours And Company | Butadiene/acrylonitrile photosensitive, elastomeric polymer compositions for flexographic printing plates |
US4537936A (en) * | 1981-04-30 | 1985-08-27 | Sumitomo Chemical Company, Limited | Diene rubber composition, method of preparing the same and tire employing said composition |
JPS61126151A (en) * | 1984-11-21 | 1986-06-13 | Nippon Zeon Co Ltd | Oil-resistant rubber composition |
-
1972
- 1972-04-24 US US00247010A patent/US3790646A/en not_active Expired - Lifetime
- 1972-04-28 IT IT23715/72A patent/IT955183B/en active
- 1972-04-28 CA CA140,887A patent/CA966597A/en not_active Expired
- 1972-05-01 GB GB2012572A patent/GB1375509A/en not_active Expired
- 1972-05-02 FR FR727215474A patent/FR2135567B1/fr not_active Expired
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4370440A (en) * | 1979-11-09 | 1983-01-25 | Polysar Limited | Compositions comprising chlorosulphonated polyethylene, carboxylated butadiene-acrylonitrile and magnesium oxide useful for liners or membranes |
DE3128993A1 (en) * | 1980-07-22 | 1982-04-08 | Japan Synthetic Rubber Co., Ltd., Tokyo | Rubber composition |
DE3248378A1 (en) * | 1981-12-28 | 1983-07-14 | Nippon Zeon Co., Ltd., Tokyo | Oil- and degradation-resistant rubber article |
US4849295A (en) * | 1987-12-11 | 1989-07-18 | Eagle-Picher Industries, Inc. | High temperature metal rubber gasket |
DE3941904A1 (en) * | 1989-12-13 | 1991-06-20 | Inst Hydravlika I Pnevmatika | Elastomer compsn. for hydraulic accumulator balloons - contains acrylonitrile]-butadiene] rubber, carbon black, DBP, zinc oxide, sulphur etc. and specified mixt. of accelerators |
EP3034518A1 (en) * | 2014-12-19 | 2016-06-22 | Lanxess Deutschland GmbH | Color stable nitrile rubbers |
WO2016096352A1 (en) * | 2014-12-19 | 2016-06-23 | Lanxess Deutschland Gmbh | Color-stable nitrile rubbers |
KR20170095862A (en) * | 2014-12-19 | 2017-08-23 | 아란세오 도이치란드 게엠베하 | Color-stable nitrile rubbers |
RU2689632C2 (en) * | 2014-12-19 | 2019-05-28 | ЛЕНКСЕСС Дойчланд ГмбХ | Colour-stable nitrile rubbers |
Also Published As
Publication number | Publication date |
---|---|
DE2221094A1 (en) | 1972-11-30 |
IT955183B (en) | 1973-09-29 |
FR2135567A1 (en) | 1972-12-22 |
FR2135567B1 (en) | 1973-07-13 |
DE2221094B2 (en) | 1976-07-08 |
CA966597A (en) | 1975-04-22 |
GB1375509A (en) | 1974-11-27 |
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